Composite materials with high Z-direction electrical conductivity

ABSTRACT

A curable composite material having high z-direction electrical conductivity. The curable composite material includes two or more layers of reinforcement carbon fibers that have been infused or impregnated with a curable matrix resin and an interlaminar region containing at least conductive nano-sized particles, e.g. carbon nanotubes, and a light-weight carbon veil. According to another embodiment, the interlaminar region further contains polymeric toughening particles. Methods for fabricating composite materials and structures are also disclosed.

This application claims the benefit of U.S. Provisional PatentApplication No. 62/053,469, filed Sep. 22, 2014, the disclosure of whichis incorporated by reference in its entirety.

BACKGROUND

In the aerospace industry, the use of fiber-reinforced polymercomposites in primary and secondary structures of aircraft is becomingmore prevalent. Composite structures are traditionally made by laying upplural layers (or plies) of resin-impregnated fibrous reinforcement(known as prepregs) on a mold surface, followed by consolidating and/orcuring. The advantages of fiber-reinforced polymer composites includehigh strength-to-weight ratio, excellent fatigue endurance, corrosionresistance and flexibility, allowing for a significant reduction incomponent parts, and reducing the need for fasteners and joints.However, the application of these materials for modern aircraft'sprimary and secondary structures presents special challenges due to thedielectric nature of the matrix resin. Although the use of carbon fibersas reinforcing fibers in composite materials can deliver some degree ofelectrical conductivity along their longitudinal direction due to theirgraphitic nature, the dielectric properties of the matrix resins in thecomposite materials reduce the overall electrical conductivity of thecomposite materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the typical current path during a lightning strike event ona composite wing box generating the “edge glow” phenomenon.

FIG. 2 shows a sealant applied at spar cap edge of the typicalconstruction of a composite wing.

FIG. 3 schematically illustrates a curable composite material withinterlaminar regions containing polymeric toughening particles,conductive nano-particles and carbon veils according to an embodiment ofthe present disclosure.

FIG. 4 schematically illustrates a particle-containing resin film and acarbon veil being laminated onto each side of a carbon fiber layer,according to an embodiment of the present disclosure.

FIG. 5 is a graphic summary of electrical conductivity data for variouscomposite laminates, showing the synergistic effect of multi-walledcarbon nanotubes (MWCNT) and carbon veil without toughening particles.

FIG. 6 is a graphic summary of electrical conductivity data for variouscomposite laminates, showing the synergistic effect of MWCNT and carbonveil with toughening particles.

FIG. 7 is a graphic summary of electrical conductivity data for variouscomposite laminates, showing the synergistic effect of carbon black andcarbon veil.

FIG. 8 is a graphic summary of Compression After Impact (CAI) data forvarious composite laminates, showing the effect of carbon veil andconductive nanoparticles.

DETAILED DESCRIPTION

Increasing the electrical conductivity of fiber-reinforced polymercomposites is desirable in order to meet the requirements for lightningstrike protection of an aircraft and to avoid a phenomenon called “edgeglow”, particularly for the composite wing assembly. The edge glowphenomenon manifests itself as a bright glow or spark in compositeskin/spar assembly with energy sufficient to be a potential ignitionsource of fuel vapors.

This edge glow phenomenon may appear during a lightning strike event,especially on composite laminates having low z-direction electricalconductivity. During a lightning strike event, a transient charge withhigh intensity current travels through the skin and then enters the wingsubstructure (e.g. structural spar or ribs) because of the fastenersconnecting the two composite parts. So typically, in a compositeskin/spar assembly, current travels partially on the skin and partiallythrough the spar which represents one of the walls of the fuel tank.

The current passes laterally from the fasteners through adjacentcomposite plies of the spar and tends to travel along the fibers becauseof the higher electrical conductivity as compared to the resin matrix.This path may generate the typical bright glow or sparks at the spar/ribcap edge, which is called “edge glow” phenomenon by those skilled in theart.

FIG. 1 shows a potential critical current path during a lightning strikeevent on a composite wing box. The edge glow phenomenon appears morecritical when the resin between the fiber reinforcement plies is highlyresistive, and consequently, the current tends not to flow betweenadjacent plies. If the z-direction electrical conductivity is too low,significant voltage drops can be produced between plies during thestrike, thus increasing the risk of edge glow.

Edge glow phenomenon is associated with electron surface ejections orplasma generation at the composite edges and often appears as a kind ofresin explosion. Uncertainty regarding the nature of this phenomenon hasposed several attentions in relation to the ignition capabilities offuel vapors during a lightning strike event.

A conventional solution is to apply a sealant at the fuel tank (see FIG.2). An example of such fuel tank sealant is the PR 1776 Class B sealantfrom Le Joint Francais, FR. However, such method leads to additionalweight and is not always effective due to the lack of standardizationand difficulties in the sealant application. Over time, the sealantbecomes ineffective due to aging, or can be totally washed off by thefuel in the tank. Moreover, a lightning strike can result in thegeneration of high pressure gasses at the cut edge which may shatter theedge seal. There remains a need for a multifunctional composite materialthat can address the edge glow issue discussed above while providinggood mechanical properties such as resistance to impact anddelamination.

It is widely accepted in the aerospace industry that two of the maindesign drivers for aircrafts composite structures are their resistanceto specific impacts and to the propagation of the damage after suchevents.

Delamination is an important failure mode for composite materials.Delamination occurs when two laminated layers de-bond from each other.Important design limiting factors include the energy needed to initiatethe delamination and the energy needed to propagate it.

The need to improve the impact resistance performance of compositestructures, especially for aircrafts primary structures, has triggeredthe development of a new generation of composite materials toughenedwith interlaminar toughening particles, often defined as “thirdgeneration composite materials”. Such technological solution provideshigh impact resistance to carbon fiber-reinforced composites but alsocreates an electrically insulating inter-laminar region between adjacentplies, resulting in a significant reduction in the overall compositestructure's electrical conductivity especially in the z-direction. The“z-direction” refers to the direction orthogonal to the plane on whichthe reinforcing fibers are arranged in a composite structure or the axisthrough the thickness of the composite structure.

The electrical conductivity of composite materials can be improved byincorporating different conductive materials, such as conductiveparticles, in the matrix resin of the fiber-reinforced polymercomposite, or in the interlaminar regions of a multilayered compositestructure, e.g. prepreg layup. For example, metallic fillers may beadded at high loadings to increase the resin electrical conductivity,but this leads to significant weight gain and reduction in impactresistance-related properties such as Compression Strength After Impact(CSAI or CAI) and interlaminar fracture toughness. As such, thestate-of-the art solutions are such that the z-direction conductivity ofa composite can be improved but not, simultaneously, its mechanicalperformance. A cured composite with improved impact performance is onewith improved CAI and fracture toughness. CAI measures the ability of acomposite material to tolerate damage. In the test for measuring CAI,the cured composite is subjected to an impact of a given energy and thenloaded in compression. The damage area and the dent depth are measuredfollowing the impact and prior to the compression test. During thistest, the composite material is constrained to ensure that no elasticinstability is taking place and the strength of the composite materialis recorded.

Fracture toughness is a property which describes the ability of amaterial containing a crack to avoid the fracture, and is one of themost important properties of a material for aerospace applications.Fracture toughness is a quantitative way of expressing a material'sresistance to brittle fracture when a crack is present.

Fracture toughness may be quantified as strain energy release rate(G_(c)), which is the energy dissipated during fracture per unit ofnewly created fracture surface area. G_(c) includes G_(Ic) (Mode1—opening mode) or G_(IIc) (Mode II—in plane shear). The subscript “Ic”denotes Mode I crack opening, which is formed under a normal tensilestress perpendicular to the crack, and the subscript “IIc” denotes ModeII crack produced by a shear stress acting parallel to the plane of thecrack and perpendicular to the crack front. The initiation and growth ofa delamination can be determined by examining Mode I fracture toughness.

In some embodiments, the combination of conductive nano-particles andlight weight carbon veil at the interlaminar region of a multilayeredcomposite material produce a synergistic effect that results in animprovement in the z-direction electrical conductivity. Furthermore,with the addition of specific polymeric toughening particles, animprovement in CAI and G_(Ic) can also be obtained. In some instances,it has been found that the combination of conductive nano-particles andcarbon veil results in z-direction electrical conductivity that is morethan 2 order of magnitude higher as compared to the unmodified versionof the same composite material without any reduction in mechanicalperformance, including CAI and delamination resistance in Mode I(G_(Ic)), and without negatively affecting the material manufactureability and process ability. Moreover, the conductivity effect obtainedfrom having the combination of conductive nano-particles and carbon veilis much greater than the sum of their individual conductivity effects.

One embodiment of the present disclosure is directed to a curablecomposite material composed of two or more layers of reinforcementfibers that have been infused or pre-impregnated with a curable orthermosettable resin. The interlaminar region between adjacent layers ofreinforcement fibers contains conductive nano-particles dispersedthroughout a curable matrix resin, polymeric toughening particles and acarbon veil embedded in the same matrix resin. The conductivenano-particles are significantly smaller in size as compared to thepolymeric toughening particles. The polymeric toughening particles maybe substantially insoluble in the matrix resin upon curing of thecomposite material, and remain as discreet particles at the interlaminarregion after curing (referred herein as “insoluble” particles). In someembodiments, the polymeric toughening particles are swellable particles,which increase in size when the surrounding resin is heated. In someembodiments, the polymeric toughening particles include both insolubleparticles and “soluble” thermoplastic particles. “Soluble” thermoplasticparticles refer to solid particles that dissolve into the surroundingmatrix resin when the mixture thereof is heated or during the curingcycle of the matrix resin, and do not remain as discreet particles inthe cured resin matrix.

The resin at the interlaminar region (without conductive nano-particles,carbon veil or toughening particles) may be the same or different fromthe matrix resin impregnating the reinforcement fibers. In someembodiments, the matrix resin impregnating the reinforcement fibers alsocontains conductive nano-particles dispersed therein.

FIG. 3 schematically illustrates a curable composite material 20according to an embodiment of the present disclosure. The compositematerial 20 contains interlaminar regions 21 a and 21 b formed betweenlayers 22, 23, 24 of reinforcement fibers that have been infused orimpregnated with a curable matrix resin. Each of the interlaminarregions 21 a and 21 b contains a curable matrix resin with conductivenano-particles 25 dispersed therein, polymeric toughening particles 26and a carbon veil 27 embedded in the same matrix resin. The compositionof the interlaminar resin (without conductive nano-particles 25,toughening particles 26, and carbon veil 27) may be similar to ordifferent from that of the matrix resin impregnating fiber layers 22,23, 24. When the interlaminar resin is similar to that of the matrixresin impregnating fiber layers 22, 23, 24, the resin matrices containone or more thermoset resins in common. The polymeric tougheningparticles 26 may be positioned side by side, and together form a singlelayer of particles. In this manner, the depth of the interlaminar regionis determined by the sizes of the particles. In some embodiments, thetoughening particles 26 are similar in size (e.g., spherical particleshaving approximately the same diameter) and the depth of theinterlaminar region is about the same or slightly greater than theaverage diameter of the toughening particles 26.

In some embodiments, the cured composite material containing thecombination of conductive nano-particles, polymeric toughening particlesand carbon veil in the interlaminar region has the following properties:electrical conductivity in the z-direction of at least about 10 S/m(Siemens per meter), for example, from about 10 S/m to about 100 S/m, asmeasured in DC conditions according to a 4-probe testing method, CAI at270 in-lbs (or 30.5 J) of at least about 35 Ksi, for example, from about35 Ksi (or about 241 MPa) to about 55 Ksi (or about 379 MPa), asmeasured in accordance with ASTM-D7137, and interlaminar fracturetoughness under mode I (G_(Ic)) of at least about 1.7 in-lb/in², forexample, from about 1.7 in-lb/in² (or about 296 J/m²) to about 5in-lb/in² (or about 870 J/m²), as measured in accordance to ASTM-D5528.

In an alternative embodiment, the interlaminar region between adjacentlayers of reinforcement fibers contains the combination of conductivenano-particles dispersed throughout a matrix resin and a carbon veilembedded in the same matrix resin, but no polymeric toughening particlesare present. As an example, the curable composite material asillustrated in FIG. 3 may be modified so that the interlaminar regions21 a and 21 b contain a curable matrix resin with dispersed conductivenano-particles 25 and the carbon veil 27, but no polymeric tougheningparticles 26. In this embodiment, the depth of the interlaminar regionis determined by the thickness of the carbon veil.

In some embodiments, the combination of conductive nano-particles andlight weight carbon veil at the interlaminar region of a multilayeredcomposite material produce a synergistic effect that results in animprovement in the z-direction electrical conductivity. In someinstances, it has been found that the combination of conductivenano-particles and carbon veil results in z-direction electricalconductivity that is more than 1 order of magnitude higher as comparedto the unmodified version of the same composite material but noreduction in mechanical performance including CAI and delaminationresistance in Mode I (G_(Ic)). Moreover, the conductivity effectobtained from having the combination of conductive nano-particles andcarbon veil is much greater than the sum of their individualconductivity effects.

In some embodiments, the cured composite material containing thecombination of conductive nano-particles and carbon veil but nopolymeric particles at the interlaminar region, has the followingproperties: electrical conductivity in the z-direction of at least about10 S/m (Siemens per meter), for example, from about 10 S/m to about 100S/m, as measured in DC conditions according to a 4-probe testing method,CAI at 270 in-lbs (or 30.5 J) of at least about 25 Ksi, for example,from about 25 Ksi (or about 172 MPa) to about 45 Ksi (or about 310 MPa),as measured in accordance with ASTM-D7137 and interlaminar fracturetoughness under mode I (G_(Ic)) of at least about 1.2 in-lb/in², forexample, from about 1.2 in-lb/in² (or about 210 J/m²) to about 3in-lb/in² (or about 522 J/m²), as measured in accordance to ASTM-D5528.

The composite material disclosed herein is a multifunctional material,which may be successfully used in those aircrafts applications wherehigh mechanical performance and high electrical conductivity arerequired. In cured state, the composite material's improved electricalconductivity can function to spread out or dissipate electric currents,such as those generated by a lightning strike, over a greater area of acomposite structure produced from the composite material, therebyreducing the likelihood of a catastrophic damage to localized portionsof the composite structure. As such, using this multifunctionalcomposite material can be an efficient solution for mitigating lightningstrike's direct effect and for preventing the edge glow phenomenon incomposites discussed above. Furthermore, the cured composite materialprovides the additional benefit of electromagnetic shielding.

Conductive Nano-Particles

The term “nano-particles” as used herein, refers to materials having atleast one dimension smaller than about 0.1 micrometer (<100 nanometers)and an aspect ratio from about 50:1 to about 5000:1. The dimensions ofthe nano-particles can be determined by a Dynamic Light Scattering (DSL)technique. For example, a nanoparticle analyzer such as SZ-100 fromHoriba may be used.

The nano-particles may be of any suitable three-dimensional shapesincluding, for example, spherical, ellipsoidal, spheroidal, discoidal,dendritic, rods, discs, cuboid or polyhedral.

The term “aspect ratio” as used herein refers to the ratio of thelongest dimension to the shortest dimension of a 3-dimensional body.When this term is used in relation to spherical or substantiallyspherical particles, the relevant ratio would be that of the largestcross sectional diameter to the smallest cross sectional diameter of thespherical body. As an example, a perfectly spherical particle would havean aspect ratio of 1:1.

In one embodiment, the nano-particles are carbon nanoparticles composedentirely or mostly of carbon atoms arranged, at the molecular scale, inpentagons or hexagons, or both. Suitable carbon nano-sized structuresfor the intended purpose herein include, but are not limited to, carbonnano-tubes, carbon nano-fibers, carbon nano-ropes, carbon nano-ribbons,carbon nano-fibrils, carbon nano-needles, carbon nano-sheets, carbonnano-rods, carbon nano-cones, carbon nano-scrolls (scroll-like shapes)and carbon nano-ohms, carbon black, graphite nano-platelets ornano-dots, graphenes, and other types of fullerene materials. Any ofthese fullerene materials may have a partial or total metallic coating.

The preferred carbon nanoparticles are carbon nano-tubes (CNTs).Typically, CNTs are tubular, strand-like structures having externaldiameters in the range of about 0.4 nm to about 100 nm, for example, theexternal diameter may be less than about 50 nm or less than about 25 nm.

The CNTs may be of any chirality. Armchair nanotubes are contemplated.Moreover, the CNTs may be semiconducting nanotubes or any other typethat displays electrical conductivity. Suitable CNTs may includesingle-walled carbon nano-tubes (SWCNTs), double-walled carbon nanotubes(DWCNTs) and multi-walled carbon nanotubes (MWCNTs). In one embodiment,the carbon nanomaterials are MWCNTs.

In another embodiment, the conductive nanoparticles may include metallicnano-particles, metal or carbon coated nano-particles and combinationsthereof, having an electrical conductivity greater than about 5×10³ S/m.Suitable metallic nano-particles include particles of any known metalsincluding, but are not limited to, silver, gold, platinum, palladium,nickel, copper, lead, tin, aluminum, titanium, alloys and mixturesthereof. In some embodiments, the metallic materials have an electricalconductivity of about 1×10⁷ S/m or higher, or about 3×10⁷ S/m or higher,for example, in the range from about 1×10⁷ S/m to about 7×10⁷ S/m.Electrical conductivity of carbon or metallic solid materials can bedetermined using four-point methods or using the eddy current methodaccording to DIN EN 2004-1 and ASTM E 1004.

Suitable organic or inorganic nano-particles which may be metal coatedinclude, but are not limited to, nanoclays, carbon nanotubes, carbonnanofibers, fullarenes, carbon nano-ropes, carbon nano-ribbons, carbonnano-fibrils, carbon nano-needles, carbon nano-sheets, carbon nano-rods,carbon nano-cones, carbon nano-scrolls and carbon nano-ohms, as well asthe corresponding boron nitride components, inorganic nanoparticles ornanofibres such as, glass nanospheres, silica nanospheres, silicananotubes, nanotitania, hollow nanoparticles, polymeric nanoparticles ornanofibers such as polyethersulfone nanofibers, polyethersulfonenanospheres, polyetherethersulfone nanofibers, polyetherethersulfonenanospheres, polyetherimide nanofibers, polyimide nanospheres, polyimidenanofibers, polyimide nanofibers, polyamide nanofibres, polyamidenanospheres, elastomeric nanospheres, polyaryletherketones (PAEK)nanofibers, polyaryletherketones nanospheres, polyphenylene sulfidenanofibers, polyamideimide nanofibers, liquid crystal polymersnanofibers.

The conductive nano-particles may be of any suitable shape andmorphology and may have a high specific surface area such as flakes,powders, fibres, spheres, dendrites, discs or any other tri-dimensionalbody with a nanometric dimension, singly or in combination. In someembodiments, the conductive nano-particles may have a specific surfacearea (SSA) of at least 0.1 m²/g, preferably 10 m²/g or higher, forexample from about 10 m²/g to about 500 m²/g as measured by standardBrunauer-Emmett-Tellermethod (BET) measurement method. For example theBET measurement method with a Micro-meritics TriStar II with thestandard nitrogen system may be used.

The conductive nano-particles for the intended purposes herein may bepresent in the range of about 0.1 wt % to about 10 wt % of the totalresin content in the composite material. In one embodiment, theconductive nano-particles are carbon nanotubes (CNTs), which are presentin an amount in the range about 0.5 wt % to about 2.0 wt % of the totalresin content. In another embodiment, the conductive nano-particles arecarbon black (CB), which are present in an amount in the range about 1.0wt % to about 6.0 wt % of the total resin content. As used herein, “wt%” refers to percentage by weight.

Carbon Veil

The carbon veil is a light-weight, nonwoven veil of randomly-arrangedfibers having an areal weight from about 1 gsm (g/m²) to about 30 gsm,including from about 2 gsm to about 10 gsm, and in some embodiments,from about 2 gsm to about 6 gsm.

The fibers of the veil are carbon fibers, which may be metal-coated.Metal coating may be of any suitable metal including, but are notlimited to, silver, gold, platinum, palladium, nickel, copper, lead,tin, aluminum, titanium, alloys and mixtures thereof.

The nonwoven veil is composed of intermingled, randomly arranged fibersand a small amount of polymeric binder for holding the fibers together.It is desirable to provide a nonwoven veil having a sufficient amount ofbinder to hold the fibers together but the binder amount is small enoughto leave the resulting veil permeable/porous to fluids such as liquidresin. To that end, the amount of binder is less than 30 wt % based onthe total weight of the veil. Typical binders include poly vinyl alcohol(PVA), polyester, polyester, styrene acrylic, vinyl-acrylic, epoxy,phenoxy, polyurethanes, polyamides, acrylates, hybrids and copolymersthereof. An example of a suitable carbon veil is Optiveil™ supplied byTechnical Fiber Products Ltd. (TFP, U.K.).

In some embodiments, the nonwoven veil is flexible and isself-supporting, meaning that it does not require a supporting carrier.Furthermore, the nonwoven veil is a single-layer material, which is notattached to another layer of fibers. The fibers of the nonwoven veil maybe chopped or continuous fiber filaments or combination thereof.

The majority of the nonwoven fibers in the veil may have cross-sectiondiameters in the range of about 0.01 to about 15 micron. In someembodiments, the major portion of the fibers is in the range of about 4to about 7 micron in diameter.

The nonwoven carbon veil discussed above may be produced by aconventional wet-laid process, as an example. In a wet-laid process, wetchopped fibers are dispersed in a water slurry that contains binder(s),and other chemical agents such as surfactant(s), viscosity modifier(s),defoaming agent(s), etc. Once the chopped fibers are introduced into theslurry, the slurry is intensely agitated so that the fibers becomedispersed. The slurry containing the fibers is deposited onto a movingscreen where a substantial portion of the water is removed to form aweb. Optionally, a liquid binder is then applied to the web. Theresulting veil is dried to remove any remaining water, and if necessary,to cure the binder(s). The resulting non-woven veil is an assembly ofdispersed, individual fiber filaments arranged in random orientation.Wet-laid processes are typically used when a uniform distribution offibers and/or weight is desired.

In one embodiment, the carbon veil is metallized with a thin layer ofmetal on at least one side as described in the published U.S. patentapplication with US Pub. No. 2011/10159764, which is incorporated hereinby reference. Alternatively, any other state of the art metallizationprocesses may be also used to produce the metal-coated veil includingphysical deposition such as sputtering, sintering, and electrolyticdeposition. In one embodiment, the metal-coated carbon veil has an arealweight of from about 2 gsm to about 30 gsm, or from about 2 gsm to about15 gsm, and a metal content of from about 5% to about 50% or from about10% to about 70% by weight based on the total weight of the veil.

Polymeric Toughening Particles

The polymeric toughening particles that are suitable for the purposesherein include thermoplastic or elastomeric particles. These polymerictoughening particles do not have a conductive coating such as metal.

In some embodiments, the polymeric toughening particles includeparticles that are substantially insoluble in the thermoset matrix resinof the composite materials during curing thereof, and remain as discreetparticles in the cured matrix resin after curing. In certainembodiments, the insoluble polymeric particles are also swellableparticles in the thermoset matrix resin of the composite material duringcuring. As discussed above, the insoluble polymeric particles may beused in combination with soluble thermoplastic particles as anadditional toughening agent.

In some embodiments, the toughening particles are uniformly dispersed inthe interlaminar region formed between adjacent layers of reinforcingfibers at a content of about 2% to about 20% by weight based on thetotal weight of the matrix resin contained in the composite material,including about 5% to about 15%, and about 8% to about 12%.

The polymeric toughening particles may be of any three-dimensionalshape, and in some embodiments, they are substantially spherical. Insome embodiments, the toughening particles have an aspect ratio of lessthan 5:1, for example, the aspect ratio may be about 1:1. With referenceto toughening particles, the term “aspect ratio” refers to the ratio ofthe largest cross sectional dimension of the particle to the smallestcross sectional dimension of the particle.

For spherical particles (with aspect ratio of approximately 1:1), themean particle size refers to its diameter. For non-spherical particles,the mean particle size refers to the largest cross sectional dimensionof the particles.

For the purposes disclosed herein, the polymeric toughening particlesmay have a mean particle size (d50) of less than about 100 μm, forexample, within the range of about 10 μm to about 50 μm, or within therange of about 15 μm to about 30 μm. The mean particle sizes asdisclosed herein can be measured by a laser diffraction technique, forexample, using Malvern Mastersizer 2000 which operates in the 0.002nanometer-2000 micron range. “d50” represents the median of the particlesize distribution, or alternatively is the value on the distributionsuch that 50% of the particles have a particle size of this value orless.

In some embodiments, the polymeric toughening particles are larger insize as compared to the conductive nano-particles. For example, the meanparticle size (d50) of the polymeric toughening particles may be atleast 100 times greater than the smallest dimension of the conductivenano-particles.

As an example, when the conductive nano-particles are carbon nanotubes,the mean particle size (d50) of the toughening particle is at least 100times greater than the diameter of the carbon nanotubes, or 1000 timesgreater.

Determining whether certain particles are insoluble or soluble relatesto the solubility of the particles in a particular resin system in whichthey reside. The resin system may include one or more thermoset resins,curing agents and/or catalysts, and minor amounts of optional additivesfor modifying the properties of the uncured or cured matrix resin.

Hot stage microscopy can be used to determine if a particle isinsoluble, partially soluble, or swellable in a resin system. First, asample of dry polymeric particles (which are not combined with a resin)is characterized by microscopy and the images analyzed using ImageJsoftware from the National Institutes of Health (Bethesda, Md., USA) todetermine the average particle size and volume. Second, a sample ofparticles is dispersed in the desired matrix resin via mechanicalmixing. Third, a sample of the resulting mixture is placed on amicroscope slide, which is then placed in a hot stage setup under amicroscope. Then, the sample is heated to the desired cure temperatureat the desired ramp rate, and any change in size, volume or shape of theparticles is continuously recorded at 10 frames per second. The diameteris normally measured for spherical particle while the longest side ismeasured in case of non-spherical ones to determine changes in size andvolume using the Image J software. All hot stage testing may be carriedout at a particle loading of 10 wt % in a matrix resin containing nocurative or catalyst.

When toughening particles are subjected to the above hot stagemicroscopy analysis and the change in diameter or volume of the particleis zero or less than 5%, as compared to the original “dry” particles,then the particle is considered to be insoluble, and not swellable. Whenthe toughening particle is subjected to the above hot stage microscopyanalysis and there is an increase in diameter or volume of the particleby more than 5%, then the particle is considered to be “swellable” aswell as insoluble. The swelling is caused by the infusion of thesurrounding resin into the outer surface of the particle.

In some embodiments, insoluble particles include particles that meltduring the hot stage microscopy analysis but are incompatible with thematrix resin, and therefore reform into discrete particles upon cooling.For analytical purposes only, the insoluble particles may flow duringthe hot stage microscopy analysis and the degree of crystallinity mayalso change.

In cases where the diameter or volume may be difficult to determine, analternate analysis may be used. A 16-ply quasi-isotropic composite panelmade from unidirectional prepreg tapes and containing a particle loadingof 10% based on the weight of the total matrix resin in the resin-richinterlaminar regions may be manufactured according to a cure schedule,and then the cured panel is cut cross-sectionally for evaluation bymicroscopy. If the particles remain as discernable, discrete particleafter curing, then the particles are considered to be insolubleparticles. If the particles fully dissolve into both the interlaminarregion and the matrix surrounding the fiber bed, and are not discernableas discrete particles upon cooling, then the particles are notconsidered insoluble interlaminar particles.

For epoxy-based matrix resin, the composition of insoluble polymericparticles may contain at least one polymer selected from: aliphaticpolyamides (PA), cycloaliphatic polyamides, aromatic polyamides,polyphthalamide (PPA), polyaryletherketones (PAEK), such aspolyetheretherketone (PEEK) and polyetherketoneketone (PEKK),polyphenylene sulfide (PPS), polyamideimide, liquid crystal polymers(LCPs), copolymers thereof, and derivatives thereof. In someembodiments, the composition of the polymeric particles contains atleast one elastomeric polymer or material selected from: cross-linkedpolybutadiene, polyacrylic, polyacrylonitrile, polystyrene, copolymersthereof, and derivatives thereof (e.g., DuoMod DP5045 sold by ZeonChemicals Inc.).

In some embodiments, the insoluble particles are insoluble thermoplasticparticles that do not dissolve during the curing process and remain asdiscreet particles within the interlaminar regions of the curedcomposite material. Examples of suitable insoluble thermoplasticparticles include polyamideimide (PAI) particles and polyamide (PA)particles (e.g. nylon), and polyphthalamide (PPA) particles, which areinsoluble in epoxy resin system during the curing cycle thereof.

Certain grades of polyimide particles may be suitable as insolubletoughening particles. For example, polyimides prepared from benzophenonetetracarboxylic acid dianhydride (BTDA), 4,4′-methylenedianiline (MDA),and 2,4-toluenediamine (TDA), and having a non-phthalimide carboncontent which contains between 90 and 92 percent aromatic carbons.

Insoluble thermoplastic particles have been found to be effective asinterlaminar tougheners for avoiding the loss of hot/wet performance.Because these thermoplastic particles remain insoluble in a matrix resineven after curing, they impart improved toughness, damage tolerance,hot/wet performance, processing, micro-cracking resistance, and reducedsolvent sensitivity to the cured resin.

The method of manufacturing the insoluble particles described herein mayinclude, in any order, emulsification, precipitation, emulsionpolymerization, washing, drying, extrusion, milling, grinding,cryo-grinding, jet milling and/or sieving the particles. Those skilledin the art will appreciate that these steps can be achieved by any ofnumerous methods known in the art.

The insoluble particles used for the intended purposes herein includecross-linked thermoplastic particles. According to one embodiment, thecross-linked thermoplastic particle is composed of a crosslinkingnetwork created by reacting one or more crosslinkable thermoplasticpolymers having one or more reactive groups with a crosslinking agentthat is chemically reactive to the reactive groups, wherein thecrosslinking agent directly crosslinks the polymer chains to each othervia the reactive groups. The reactive groups may be end groups orpendant groups on the polymer backbone. The direct crosslinking reactionof this embodiment may be described as “tying-up” the polymer moleculesvia direct crosslinking of the polymer chains using one or more reactivegroups.

The above crosslinked thermoplastic particles may be produced by theprocess described in U.S. Patent Application with Publication No.2010/0304118, published on Dec. 2, 2010, which is incorporated herein byreference. This method includes dissolving a thermoplastic polymer withreactive functional groups, a crosslinking agent, and a catalyst into acommon solvent, which is immiscible with water. An emulsion is thencreated in water by using a non-ionic surfactant, whereby emulsifiedparticles are formed. The emulsified particles are subsequently driedand cured so that the polymeric chains become chemically crosslinked.The reacting conditions and the type of crosslinking agent willdetermine the final properties of the particles. Reacting conditionssuch as temperature result in greater crosslinking. Crosslinking agentswith two or more reactive sites (i.e. functional groups) are preferred.The resulting crosslinked thermoplastic particles are discreet,free-moving particles that may be added to a curable resin. Thesecrosslinked thermoplastic particles are also swellable in the curableresin during curing.

Examples of suitable thermoplastic polymers bearing reactive groups thatare susceptible to crosslinking include, but are not limited to, one ormore of a polyether, polycarbonate, polyetherimide (PEI), polyamide,polyimide, polysulfone, polyethersulfone (PES), poly phenylene oxide(PPO), poly ether ketones, polyaryletherketones (PAEK) such aspolyetheretherketone (PEEK) and polyetherketoneketone (PEKK), polyphenylsulfides (PPS), polyhydroxyethers, styrene-butadiene, polyacrylates,polyacetol, polybutyleneterephthalate, polyamide-imide,polyetherethersulfone (PEES), blends thereof, or a copolymer thereof,PES homopolymers (such as SUMIKAEXCEL 5003P from Sumitomo Chemical Co.or Radel® PES from Solvay), or PEES homopolymers. Specific examples ofPES copolymers include PES/PEES copolymer with various repeat unitratios. The thermoplastics listed above can be used as a singlecomponent to form a particle, or, when more than one thermoplasticpolymer is used, a hybrid structure, or a hybrid particle, is formed.

In other embodiments, the crosslinked thermoplastic particles are formedfrom a blend of thermoplastic polymers. In still other embodiments, thecrosslinked particles described herein may be formed from a hybridstructure wherein two or more thermoplastic polymers are used.

The reactive groups on crosslinkable thermoplastic polymers may be oneor more of the following: amine; hydroxyl; anhydride; glycidyl;carboxylic acid; maleimide; isocyanate; phenolic; nadimide; cyanateester; acetylene; vinyl; vinyl ester; diene; or derivatives thereof. Insome cases, unsaturations on the polymer chain might serve ascross-linking points (for acrylic and methacrylic family as well someinsaturated rubbers, vinyl esters or unsaturated polyesters). The numberof reactive groups may be a minimum of one reactive group per chain and,in some embodiments, is considered as the lowest fraction necessary tocreate a connected polymer backbone; a number around or greater than oneis preferred to produce a tightly cross-linked polymer orinter-penetrating network. Polymers with functionalities greater than 2will easily produce highly reacted gels.

Depending on the chemical nature of the thermoplastic polymer's endgroups/functionalities, an appropriate multifunctional crosslinkingagent with multiple reactive sites may be selected. Examples of suchcrosslinking agents are: alkylated melamine derivatives (e.g. CYMEL®303), acid chlorides (e.g. 1,3,5 benzenetricarbonyl trichloride),multi-functional epoxies (e.g. ARALDITE® MY0500, MY721), carboxylicacids (e.g. benzenetetracarboxylic acid).

In another embodiment, the crosslinked thermoplastic particle iscomposed of an inter-penetrating polymer network (IPN), which iscomposed of thermoplastic polymer chains intertwined with an independentcrosslinking network. The IPN is created by reacting one or morecompounds (e.g. crosslinkable monomers or polymers) having one or morereactive groups with a cross-linking agent that is chemically reactiveto the reactive groups in the presence of a thermoplastic polymer. Thereaction (which occurs under certain crosslinking or curing conditions)causes the compounds to become cross-linked via the reactive groups,thereby forming an independent cross-linking network. As such, thethermoplastic polymer chains are intertwined with the independentcross-linking network at a molecular level to form an IPN. This approachmay be described as “tying-up” the thermoplastic polymer chains via theformation of a separate and independent crosslinking network, therebycreating an inter-penetrating network. Thus, in this embodiment, thethermoplastic polymer does not need to have reactive groups thereon.This type of crosslinked particles may be produced by the processdescribed in U.S. Pat. No. 8,846,818, the content of which isincorporated herein by reference. The resulting crosslinkedthermoplastic particles are discreet particles that may be added to acurable resin. These crosslinked thermoplastic particles are alsoswellable in the curable resin during curing.

As an example, a crosslinked particle with an IPN may be created by: (i)forming an emulsion containing a thermoplastic polymer, amultifunctional epoxy resin and an amine curing agent capable ofcross-linking the epoxy resin; (ii) removing the solvent from theemulsion and collecting the condensate, which is in the form of solidparticles; (iii) drying the particles followed by curing (e.g. byheating) so that the epoxy resin becomes cross-linked. As a result ofcuring, the cross-linked epoxy forms an IPN with the thermoplasticpolymer in each particle.

The swellable, crosslinked thermoplastic particles also form a “gradientinterface” with the surrounding matrix resin in which they reside duringcuring. The term “gradient interface” as used herein refers to thegradual and strong interface between each of the particles and thesurrounding matrix resin. A gradient interface is achieved by usingengineered crosslinked thermoplastic particles that arethermodynamically compatible with the thermoset resin, e.g. epoxy. Theconcentration of thermoplastic polymer in the core of a crosslinkedthermoplastic particle is greatest at the center and gradually decreasestowards the outer surface of the particle as the matrix resin enters theparticle from the outer surface and moves towards the core. This gradualdecrease in the thermoplastic concentration from the core to the outersurface of the thermoplastic particle forms the gradient interfacebetween each of the thermoplastic particles and the surrounding matrixresin. Thus, there is no sharp delineation or transition between thethermosetting resin and the thermoplastic particle. If a sharpdelineation or transition was present, the interface between thethermoplastic and the thermosetting resin would be much weaker in acomposite material in comparison to a composite material containing agradient interface. As such, these crosslinked thermoplastic particlesare considered “swellable” because the resin, which surrounds theparticle, diffuses into the particles through the particle's outersurface when the resin is heated and its viscosity is reduced, therebyresulting in an increase in the particle size. However, the crosslinkedparticles will remain as discrete and discernable particles after curingof the resin.

The crosslinked thermoplastic particles described herein are discreet,free-moving particles (i.e. in divided state) that may be added to athermosettable resin, such as an epoxy-based resin, and they arechemically cross-linked in order to prevent their total dissolution inthe resin during the cure cycle of the resin. Furthermore, they aredesigned to be thermodynamically compatible with the thermoset resin.

“Discrete particle” as used herein refers to a particle which isdiscernible in a matrix resin, and which may be detected by usingScanning Electron Microscopy (SEM), Optical Microscopy, or DifferentialInterference Contrast microscopy (DIC).

When used, soluble thermoplastic particles include particulatethermoplastic polymers selected from: polyarylsulfones, e.g.polyethersulfone (PES), polyetherethersulfone (PEES), polyetherimide(PEI) and polyimides (PI). As mentioned previously, these solublethermoplastic particles are solid particles (e.g. powder) that dissolveinto the surrounding resin matrix when the mixture thereof is heated orduring the curing cycle of the matrix resin, and do not remain asdiscreet particles in the cured matrix resin. As used herein,“dissolves” into the surrounding resin means forming a homogeneous orcontinuous phase with the resin.

Matrix Resin

The curable matrix resin (or resin composition) forimpregnating/infusing the reinforcement fibers is a hardenable orthermosettable resin containing one or more uncured thermoset resins,which include, but are not limited to, epoxy resins, imides (such aspolyimide and bismaleimide), vinyl ester resins, cyanate ester resins,isocyanate modified epoxy resins, phenolic resins, benzoxazines,formaldehyde condensate resins (such as urea, melamine and phenol),unsaturated polyesters, hybrids, blends and combinations thereof.

Suitable epoxy resins include polyglycidyl derivatives of aromaticdiamine, aromatic mono primary amines, aminophenols, polyhydric phenols,polyhydric alcohols, polycarboxylic acids. Examples of suitable epoxyresins include polyglycidyl ethers of the bisphenols such as bisphenolA, bisphenol F, bisphenol S and bisphenol K; and polyglycidyl ethers ofcresol and phenol based novolacs.

Specific examples are tetraglycidyl derivatives of4,4′-diaminodiphenylmethane (TGDDM), resorcinol diglycidyl ether,triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, bromobisphenol Fdiglycidyl ether, tetraglycidyl derivatives of diaminodiphenylmethane,trihydroxyphenyl methane triglycidyl ether, polyglycidylether ofphenol-formaldehyde novolac, polyglycidylether of o-cresol novolac ortetraglycidyl ether of tetraphenylethane.

Commercially available epoxy resins suitable for use in the matrix resininclude N,N,N′,N′-tetraglycidyl diamino diphenylmethane (e.g. MY 9663,MY 720, and MY 721 from Huntsman);N,N,N′,N′-tetraglycidyl-bis(4-aminophenyl)-1,4-diiso-propylbenzene (e.g.EPON 1071 from Momentive);N,N,N′,N′-tetraclycidyl-bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene,(e.g. EPON 1072 from Momentive); triglycidyl ethers of p-aminophenol(e.g. MY 0510 from Hunstman); triglycidyl ethers of m-aminophenol (e.g.MY 0610 from Hunstman); diglycidyl ethers of bisphenol A based materialssuch as 2,2-bis(4,4′-dihydroxy phenyl) propane (e.g. DER 661 from Dow,or EPON 828 from Momentive, and Novolac resins preferably of viscosity8-20 Pa·s at 25° C.; glycidyl ethers of phenol Novolac resins (e.g. DEN431 or DEN 438 from Dow); di-cyclopentadiene-based phenolic novolac(e.g. Tactix 556 from Huntsman); diglycidyl 1,2-phthalate (e.g. GLY CELA-100); diglycidyl derivative of dihydroxy diphenyl methane (BisphenolF) (e.g. PY 306 from Huntsman). Other suitable epoxy resins includecycloaliphatics such as 3′,4′-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate (e.g. CY 179 from Huntsman).

Generally, the curable matrix resin contains one or more thermosetresins, and may be in combination with other additives such as curingagents, curing catalysts, co-monomers, rheology control agents,tackifiers, inorganic or organic fillers, thermoplastic and/orelastomeric polymers as toughening agents, stabilizers, inhibitors,pigments, dyes, flame retardants, reactive diluents, and other additiveswell known to those skilled in the art for modifying the properties ofthe matrix resin before or after curing.

Suitable toughening agents for the curable matrix resin compositioninclude but are not limited to homopolymers or copolymers either aloneor in combination of polyamides, copolyamides, polyimides, aramids,polyketones, polyetherimides (PEI), polyetherketones (PEK),polyetherketoneketone (PEKK), polyetheretherketones (PEEK),polyethersulfones (PES), polyetherethersulfones (PEES), polyesters,polyurethanes, polysulphones, polysulphides, polyphenylene oxide (PPO)and modified PPO, poly(ethylene oxide) (PEO) and polypropylene oxide,polystyrenes, polybutadienes, polyacrylates, polymethacrylates,polyacrylics, polyphenylsulfone, high performance hydrocarbon polymers,liquid crystal polymers, elastomers and segmented elastomers.

The addition of curing agent(s) and/or catalyst(s) in the curable matrixresin is optional, but the use of such may increase the cure rate and/orreduce the cure temperatures, if desired. The curing agent is suitablyselected from known curing agents, for example, aromatic or aliphaticamines, or guanidine derivatives. An aromatic amine curing agent ispreferred, preferably an aromatic amine having at least two amino groupsper molecule, and particularly preferable are diaminodiphenyl sulphones,for instance where the amino groups are in the meta- or in thepara-positions with respect to the sulphone group. Particular examplesare 3,3′- and 4-,4′-diaminodiphenylsulphone (DDS); methylenedianiline;bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene;bis(4-aminophenyl)-1,4-diisopropylbenzene;4,4′methylenebis-(2,6-diethyl)-aniline (MDEA from Lonza);4,4′methylenebis-(3-chloro, 2,6-diethyl)-aniline (MCDEA from Lonza);4,4′methylenebis-(2,6-diisopropyl)-aniline (M-DIPA from Lonza);3,5-diethyl toluene-2,4/2,6-diamine (D-ETDA 80 from Lonza);4,4′methylenebis-(2-isopropyl-6-methyl)-aniline (M-MIPA from Lonza);4-chlorophenyl-N,N-dimethyl-urea (e.g. Monuron);3,4-dichlorophenyl-N,N-dimethyl-urea (e.g. DIURON™) and dicyanodiamide(e.g. AMICURE™ CG 1200 from Pacific Anchor Chemical).

Suitable curing agents also include anhydrides, particularlypolycarboxylic anhydrides, such as nadic anhydride, methylnadicanhydride, phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,endomethylenetetrahydrophtalic anhydride, and trimellitic anhydride.

The curable matrix resin at the interlaminar region is also a hardenableor thermosettable resin containing one or more uncured thermoset resinsof the type discussed above. In certain embodiments, the curable matrixresin at the interlaminar region is the same as the matrix resin in theregion containing the reinforcement fibers. In other embodiments, theresin at the interlaminar region is different from the matrix resin inthe region containing the reinforcement fibers.

Reinforcement Fibers

The reinforcement fibers for the purposes herein include carbon orgraphite fibers with a high tensile strength, for example, greater than500 ksi (or 3447 MPa). The reinforcement fibers may be in the form ofcontinuous tows made up of multiple filaments, as continuousunidirectional or multidirectional fibers, as woven fabrics ormultiaxial fabrics. Unidirectional fibers refer to fibers that run (orextend) in one direction only. Mutiaxial fabrics include non-crimpedfabrics. In some embodiments, the reinforcement fibers are in the formof unidirectional fibers or woven fabric, not a nonwoven layer.Moreover, the carbon fibers may be sized or unsized.

For structural applications, the content of the reinforcement fibers ina prepreg or composite material may be within the range 30% to 70% byvolume, in some embodiments, 50% to 70% by volume.

Manufacturing of Composite Prepregs and Laminates

The term “prepreg” as used herein refers to a sheet or layer of fibersthat has been impregnated with a curable resin composition within atleast a portion of the fibrous volume. The prepreg used formanufacturing aerospace structures is usually a resin-impregnated sheetof uni-directional reinforcing fibers, e.g. carbon fibers, which isoften referred to as “tape” or “uni-directional tape”. The prepregs maybe fully impregnated prepregs or partially impregnated prepregs. Thematrix resin impregnating the reinforcement fibers may be in a partiallycured or uncured state. The term “impregnated” as used in herein refersto fibers that have been subjected to an impregnation process wherebythe fibers are at least partially surrounded by or embedded in a matrixresin.

Typically, the prepreg is in a pliable or flexible form that is readyfor laying up and molding into a three-dimensional configuration,followed by curing into a final composite part/structure. This type ofprepregs is particularly suitable for manufacturing load-bearingstructural parts, such as wings, fuselages, bulkheads and controlsurfaces of aircrafts. Important properties of the cured prepregs arehigh strength and stiffness with reduced weight.

To form a composite structure, a plurality of prepreg plies may be laidup on a tool in a stacking sequence to form a “prepreg lay-up.” Theprepreg plies within the layup may be positioned in a selectedorientation with respect to one another, e.g. 0°, ±45°, 90°, etc.Prepreg lay-ups may be manufactured by techniques that may include, butare not limited to, hand lay-up, automated tape layup (ATL), advancedfiber placement (AFP), and filament winding.

According to one embodiment, specific amounts of conductivenano-particles and polymeric toughening particles are mixed with acurable resin composition prior to the impregnation of carbonreinforcement fibers (i.e. prior to the prepreg manufacturing). In thisembodiment, a resin film is manufactured first by coating theparticle-containing resin composition onto a release paper. Next, one ortwo of such resin film is/are laminated onto one or both sides of alayer of carbon fibers under the aid of heat and pressure to impregnatethe fibers, thereby forming a resin-impregnated fiber layer (or prepregply) with specific fiber areal weight and resin content. During thelaminating process, the toughening particles are filtered out and remainexternal to the fiber layer due to the fact that the size of theparticles is larger than the spacing between the fiber filaments.Subsequently, two or more prepreg plies containing toughening particlestherein are laid up one on top of the other to form a composite layupwith placement of a nonwoven carbon veil between adjacent prepreg plies.As the result of the layup process, the polymeric toughening particlesand the carbon veil are positioned in the interlaminar region betweentwo adjacent carbon fiber layers. When the layup is consolidated withthe application of pressure, at least some polymeric tougheningparticles and at least some conductive nano-particles penetrate throughthe carbon veil due to the thickness and porous characteristics of thecarbon veil. Upon curing, the carbon veil becomes embedded in the matrixresin at the interlaminar region. In this embodiment, the matrix resinat the interlaminar region is the same as the matrix resin impregnatingthe reinforcement fibers, and the conductive nano-particles areuniformly dispersed throughout the matrix resin.

In another embodiment, which is schematically illustrated in FIG. 4, acurable resin film 41, which contains conductive nano-particles andpolymeric toughening particles, and a carbon veil 42 are laminated ontoeach side of a carbon fiber layer 43 such that the veil 42 is sandwichedbetween each resin film 41 and the carbon fiber layer 43. Lamination iscarried out under the aid of heat and pressure to impregnate the fibers,thereby forming a prepreg ply with specific fiber areal weight and resincontent. During the laminating process, the polymeric particles arefiltered out and remain external to the carbon fiber layer, and at leastsome polymeric particles and at least some conductive nanoparticlespenetrate through the veil. A plurality of such prepreg plies are laidup to form a composite laminate with carbon veils, conductivenano-particles and polymeric particles embedded in the interlaminarregions.

In an alternative embodiment, the method described with reference toFIG. 4 is modified so that the curable resin film 41 contains dispersedconductive nanoparticles, but not polymeric toughening particles. Theresulting composite laminate then contains carbon veils and conductivenano-particles embedded in the interlaminar regions.

According to a further embodiment, specific amounts of conductivenano-particles are mixed with a curable resin composition prior to theimpregnation of carbon reinforcement fibers (i.e. prior to the prepregmanufacturing). In this embodiment, a resin film is manufactured firstby coating the particle-containing resin composition onto a releasepaper. Next, one or two of such resin film is/are laminated onto one orboth sides of a layer of carbon fibers under the aid of heat andpressure to impregnate the fibers, thereby forming a resin-impregnatedfiber layer (or prepreg ply) with specific fiber areal weight and resincontent. Subsequently, two or more prepreg plies are laid up, one on topof the other, to form a composite layup with placement of a nonwovencarbon veil between adjacent prepreg plies. As the result of the layupprocess, the carbon veil is positioned in the interlaminar regionbetween two adjacent carbon fiber layers. When the layup isconsolidated, at least some conductive nano-particles penetrate throughthe carbon veil due to the thickness and porous characteristics of thecarbon veil. Upon curing, the carbon veil becomes embedded in the matrixresin at the interlaminar region. In this embodiment, the matrix resinat the interlaminar region is the same as the matrix resin impregnatingthe reinforcement fibers, and the conductive nano-particles areuniformly dispersed throughout the matrix resin.

Curing of the composite material or prepreg layup disclosed herein maybe carried out at elevated temperatures of up to about 200° C., forexample, in the range of about 170° C. to about 190° C., and optionally,with application of elevated pressure to restrain deforming effects ofescaping gases, or to restrain void formation. Suitable pressure may beup to 10 bar (1 MPa), for example, in the range of about 3 bar (0.3 MPa)to about 7 bar (0.7 MPa). In some embodiments, the cure temperature isattained by heating at up to 5° C./min, for example, 2° C./min to 3°C./min and is maintained for the required period of up to 9 h, or up to6 h, for example, between 2 h and 4 h. The use of a catalyst in thematrix resin may allow even lower cure temperatures. Pressure may bereleased throughout, and temperature may be reduced by cooling at up toabout 5° C./min, for example, up to 3° C./min. Post-curing attemperatures in the range of 190° C. to 350° C. and atmospheric pressuremay be performed, employing suitable heating rates to improve the glasstransition temperature of the matrix resin.

Applications

The resin compositions described herein can be used to manufacture castor moulded structural materials, and are particularly suitable forfabrication of fiber-reinforced load-bearing or impact-resistingcomposite structures with improved volume electrical conductivity.

The composite materials disclosed herein are applicable to themanufacture of components for transport applications, includingaerospace, aeronautical, nautical and land vehicles, automotive, andrailroad. For examples, the composite materials may be used forfabricating primary and secondary aircraft structures, space andballistics structures. Such structural components include composite wingstructures. The composite materials disclosed herein also find utilityin building and construction applications, as well as other commercialapplications. Notably, the composite materials are particularly suitablefor the fabrication of load-bearing or impact-resisting structures.

EXAMPLES

Measurement Methods

Composite samples manufactured in the following Examples were testedaccording to the following procedures for measuring the z-directionelectrical conductivity and mechanical properties.

Electrical Conductivity Measurements

Test sample's dimensions and tolerances are defined in Table 1.

TABLE 1 Conductivity coupons dimension Length (L)  1.0 inch Width (w) 1.0 inch Thickness (t) 0.110 inch

Sample's surfaces were polished to remove the resin excess; then silverpaste was used to create two electrodes on the opposite surfaces.Samples were clamped between two copper plates to reduce contactresistance between the wires and the sample surfaces.

Z-direction DC electrical conductivity was determined using the Keithley6221/2182A DELTA MODE system according to the 4-probes Volt-amperometricmeasurement method.

Test samples (1 inch×1 inch) were prepared and tested by applying 10 mAcurrent. Potential voltage values between the electrodes were recordedafter stabilizing the current within 2%. Z-direction resistivity andconductivity were calculated according to the following formulas:Resistivity (ρ)[ohm−m]=(V/I)/t·AConductivity (σ)(S/m)=1/ρwhere:V=potential voltage (volts)I=forced current (amperes)T=thickness of the sample which is the z dimension (m)A=cross-sectional area which is X by Y dimensions (m²)

Measurements were performed at 25° C. in standard humidity conditions.Average and corresponding standard deviation results were reported.

Mechanical Characterization

Tests for measuring mechanical performance were performed in accordancewith the methods reported in Table 2.

TABLE 2 Mechanical Tests and Corresponding Test Method Testing UnitProperty Conditioning temperature Lay-up measure Standard CAI — RT[+/0/−/90]3s Ksi ASTM-D7136 230 in-lbs and CAI — RT [+/0/−/90]3s KsiASTM-D7137 270 in-lbs G_(IC) - DCB — RT [0]₂₀ in-lb/in² ASTM-D5528 2week water 70° C. (158° F.) [0]₂₀ in-lb/in² soak @160° F. Open Hole — RT[+/90/−/0]_(2S) Ksi ASTM-D5766 Tension — −59° C. (−75° F.)[+/90/−/0]_(2S) Ksi (OHT) Open Hole — RT dry [+/90/−/0]_(2S) KsiASTM-D6484 Compression 2 week water 82° C. (180° F.) [+/90/−/0]_(2S) Ksi(OHC) soak @160° F. In-plane — RT [+45/−45]_(s) Msi ASTM-D3518 ShearSoak in MEK RT [+45/−45]_(s) Msi modulus Soak in Water RT [+45/−45]_(s)Msi (IPSM) RT in Table 2 denotes room temperature.

Example 1

Four different resin compositions were prepared based on theformulations disclosed in Table 3. Control 1.1 and Control 2.1 are twobaseline resin systems with and without interlaminar particles, andResin 1.0 and Resin 2.0 are two MWCNT-modified versions thereof. Thecompositions are reported in weight by weight (w/w) percentages.

TABLE 3 Resin Compositions Resin code Control Control Components Resin1.0 Resin 2.0 Resin 1.1 Resin 2.1 Araldite ® PY306 26.00 22.93 26.7422.93 Araldite ® MY0510 26.00 22.93 26.74 22.93 SUMIKAEXCEL 5003P 19.4617.15 19.44 17.15 MWCNT 1.45 1.27 — — TGP3551 — 3.69 — 3.69 CrosslinkedTP — 3.69 — 3.69 particles P84 — 4.62 — 4.62 4,4′DDS 27.09 23.89 27.0823.89

Araldite® PY306 is a Bisphenol F diglycidlyl ether resin available fromHuntsman,

Araldite® MY0510 is a triglycidyl ether of p-aminophenol resin availablefrom Huntsman,

SUMIKAEXCEL 5003P is a polyethersulfone polymer available from SumitomoChemical Co.,

MWCNT refers to multi-walled carbon nanotubes having an average diameterof 15 nm, and an average length of about 1 mm,

TGP3551 refers to Vestasint® TGP3551 a polyamide powder from Evonikwhich is insoluble upon curing,

P84 particles are aromatic polyimide particles from Evonik with anaverage particle size distribution d50 of 44 microns, which swell andsolubilize into the resin upon curing,

crosslinked TP particles are particles of cross-linked PES-PEES with amean particle size of 25 microns from Cytec Industries Inc., and

4,4′DDS refers to 4,4′-diaminodiphenylsulphone.

The predetermined amount of MWCNT was dispersed in the epoxy resinmixture. Then the remaining components were added to the master-batchand mixed until a homogeneous mixture was obtained.

The resin compositions were then used to produce four differentunidirectional (UD) prepregs using a hot melt impregnation process. Theresin films were produced by coating the resin composition onto arelease paper. Next, two of such resin films were laminated onto bothsides of a continuous layer of unidirectional carbon fibers (IM65E fromToho Tenax, USA), under the aid of heat and pressure, to form a prepreg.The characteristics of the prepregs are shown in Table 4. Percentage (%)shown is weight percentage.

TABLE 4 Prepregs Interlaminar Resin MWCNT particles FAW Content Prepregcode Resin code (%) (%) (gsm) (%) 3.0 1.0 1.2 0 187.97 28.87 4.0 2.0 1.212 189.68 31.15 Control 3.1 Control 1.1 0 0 191.75 32.05 Control 4.1Control 2.1 0 12 191.50 33.22

Composite laminates were manufactured by laying up the prepregs to formlay-ups with quasi-isotropic configuration (each layup being about 0.110inch thick) followed by consolidation and curing in an autoclave for 2hours at 177° C. Some laminates were produced according to the sameprocedure but a single 4 gsm nonwoven carbon veil was pressed onto oneside of the prepreg prior to laying up so that the carbon veil was aninterleaf between two adjacent prepregs.

Each nonwoven carbon veil was composed of intermediate modulus carbonfibers, and was manufactured using a wet laid (i.e. paper-making)process and an emulsion of epoxy-urethane copolymer as the binder. Thecarbon veil was very thin and porous such that the thermoplasticparticles, when present, penetrated through the veil duringconsolidation of the layups.

The z-direction electrical conductivity of the cured laminates wasmeasured and the results are reported in Table 5. Percentage (%) shownis weight percentage.

TABLE 5 Z-direction Conductivity Results Laminate MWCNT VeilInterlaminar Conductivity code Prepreg code (%) (gsm) particles (S/m)Control 5.0 Control 3.1 0 — NO 0.77 ± 0.20 Control 6.0 Control 4.1 0 —YES 0.07 ± 0.01 5.1 3.0 1.2 — NO 15.30 ± 0.85  6.1 4.0 1.2 — YES 5.54 ±0.27 5.2 3.1 0 4 NO 8.01 ± 0.63 6.2 4.1 0 4 YES 11.07 ± 1.66  5.3 3.01.2 4 NO 65.22 ± 3.85  6.3 4.0 1.2 4 YES 31.46 ± 2.87 

The results demonstrate that the combination of carbon nanotubes andcarbon veil can yield improvements in the z-direction conductivity ofthe cured laminates well above what would be expected by summing theconductivity values obtained for resin systems modified by only one ofthe two carbon materials separately.

For laminates without interlaminar toughening particles, Laminate 5.3has a z-direction conductivity value of 65.22 S/m, which is much greaterthan the sum of conductivity values of Laminate 5.1 with MWCNT only(15.3 S/m) and Laminate 5.2 with carbon veils only (8.01 S/m). FIG. 5 isa graphic summary of the z-direction conductivity results reported inTable 5, showing the synergistic effect of MWCNT and carbon veil withouttoughening particles.

For laminates with interlaminar toughening particles, a z-directionconductivity value of 31.46 S/m was measured for Laminate 6.3. Thisvalue is greater than the sum of the conductivity values of Laminate 6.1with MWCNT only (5.54 S/m) and Laminate 6.2 which contained carbon veilsonly (11.07 S/m). FIG. 6 is a graphic summary of the z-directionconductivity results reported in Table 5, showing the synergistic effectof MWCNT and carbon veil with the presence of toughening particles.

It is believed that the high conductivity values obtained for Laminates5.3 and 6.3 are the result synergistic effects between the conductiveveil and MWCNT. Such positive interactions are evident in compositematerials with and without interlaminar toughening particles.Furthermore, the presence of carbon veil and MWCNT resulted in awell-defined interlaminar region between adjacent layers of structuralfibers. This effect also reduced the coefficient of variability (COV) ofthe electrical measurements.

Example 2

Three different resin compositions were prepared according to theformulations disclosed in Table 6. Compositions are reported in weightby weight (w/w) percentage. Control 7.0 is a baseline particle-toughenedresin system; Resin 7.1 and Resin 7.2 are carbon-modified versionsthereof. Relatively low concentrations of carbon fillers were selectedto produce formulations with a rheological profile suitable for standardprepreg manufacturing processes.

TABLE 6 Resin Compositions (%) Resin code Components Control 7.0 Resin7.1 Resin 7.2 Araldite ® PY306 24.07 24.1 24.1 Araldite ® MY0510 24.0724.1 24.1 SUMIKAEXEL 5003P 16.96 17.0 17.0 4,4′DDS 21.90 21.9 21.9Vestamid ® Z2649 13.00 13.0 13.0 Carbon black — — 3.0 MWCNT — 0.5 —

Vestamid® Z2649 is a polyamide 10,10 powder from Evonik which isinsoluble upon curing in the resin system. The carbon black used wasEnsaco 250 supplied by Timcal, UK.

The predetermined amount of carbon fillers (MWCNT or carbon black) wasfirst dispersed in the epoxy components. Then the remaining componentswere added to the master-batch and mixed until a homogeneous mixture wasobtained.

The three resin compositions were then used to produce differentunidirectional (UD) prepregs via a hot-melt impregnation process. Thecharacteristics of the prepregs are shown in Table 7.

TABLE 7 Prepregs Resin Prepreg Resin Optiveil ® FAW content code Code (4gsm) (gsm) (%) Control 8.0 Control 7.0 No 190.30 33.25 Control 9.0Control 7.0 Yes 194.50 33.78 8.1 7.1 No 190.05 33.98 9.1 7.1 Yes 194.7034.55 8.2 7.2 No 190.31 33.59 9.2 7.2 Yes 194.33 33.64

Composite laminates were manufactured by laying up the prepregs to form0.118 inch-thick layups with quasi isotropic configuration followed bycuring in an autoclave for 2 hours at 180° C. Some laminates wereproduced with a single 4 gsm nonwoven carbon veil (Optiveil® fromTechnical Fibre Products) as an interleaf between two adjacent prepregs.The z-direction conductivity of the cured laminates was measured and theresults are reported in Table 8.

TABLE 8 Z-direction Electrical Results Laminate Prepreg CarbonOptiveil ® Conductivity code code MWCNT black (4 gsm) (S/m) Control 10.08.0 No No No 0.05 ± 0.02 Control 11.0 9.0 No No Yes 7.42 ± 0.32 10.1 8.1Yes No No 0.57 ± 0.16 11.1 9.1 Yes No Yes 12.17 ± 0.61  10.2 8.2 No YesNo 0.26 ± 0.07 11.2 9.2 No Yes Yes 18.09 ± 0.97 

It was observed that the addition of relatively low concentrations ofcarbon nanotubes or carbon black can only yield moderate improvements inthe z-direction conductivity of cured laminates as shown for Laminate10.1 (0.57 S/m) and Laminate 10.2 (0.26 S/m). When only a carbon veilwith low areal weight is used to modify a particle toughened prepreg(Control 11.0), some improvement can be achieved (conductivity=7.42S/m). Notably, when the combination of carbon fillers and carbon veilwas used, the improvement in the z-direction conductivity of the curedlaminate was well above what would be expected by summing theconductivity value of a laminate modified with carbon fillers only andthat of a laminate modified with carbon veil only.

Referring to Table 8, Laminate 11.1 (carbon veil+MWCNT) yielded az-direction conductivity of 12.17 S/m which is approximately 50% greaterthan the expected cumulative value (7.99 S/m) of Control 11.0 (veilonly) and Laminate 10.1 (MWCNT only).

The same trend was observed for resin systems modified with carbonblack. Laminate 11.2 yielded a z-direction electrical conductivity of18.09 S/m, which is more than double the expected cumulative value (7.68S/m) of Control 11.0 (veil only) and Laminate 10.2 (carbon black only).

FIG. 7 is a graphic summary of the z-direction conductivity resultsreported in Table 8, showing the synergistic effect of carbon veil andcarbon black. It is believed that the high conductivity values measuredfor Laminates 11.1 and 11.2 are the result of a positive synergy betweenthe light-weight carbon veil and the conductive nanoparticles in theinterlaminar region of the cured laminates. The synergy may be theresult of an in-situ formation of a conductive nano-network within aconductive carbon fibers micro network upon curing.

Mechanical testing of the cured laminates was carried out and theresults are reported in Table 9.

TABLE 9 Mechanical results Laminate code Control Control Property 10.011.0 10.1 11.1 10.2 11.2 CAI 230 in-lbs (Ksi) 45.28 44.01 41.90 42.1544.11 42.66 CAI 270 in-lbs (Ksi) 41.59 40.24 39.25 40.32 44.61 40.32G_(IC) - DCB (in-lb/in²) 1.59 2.83 1.80 2.98 1.73 2.39 OHT @RT (Ksi)80.04 79.74 79.60 77.66 78.77 79.86 OHT @−75° F. (Ksi) 75.76 71.88 77.2576.23 73.27 77.94 OHC @RT (Ksi) 52.74 48.54 50.65 N.A. 53.75 50.68 OHC@180° F. (Ksi) 36.52 36.99 37.02 N.A. 37.84 38.85 IPSM @RT (Msi) 0.700.75 0.66 0.74 0.63 0.75 IPSM_((MEK))(Msi) 0.64 0.69 0.59 0.68 0.57 0.71IPSS (_(H2O))(Msi) 0.64 0.69 0.60 0.67 0.58 0.69

The results demonstrate that the combination of light-weight carbon veiland nanoparticles did not produce any significant variation in thecomposite's mechanical performance. FIG. 8 shows a graphic summary ofthe results for CAI at 230 in-lbs impact reported in Table 9. As can beseen from FIG. 8, the CAI values were not substantially affected by thepresence of the carbon veil or conductive nanoparticles.

What is claimed is:
 1. A curable composite material comprising: at leasttwo layers of reinforcement carbon fibers impregnated with a curablematrix resin; and an interlaminar region formed between adjacent layersof reinforcement carbon fibers, the interlaminar region comprising (i) acurable matrix resin that is the same as or different from the matrixresin impregnating the reinforcement carbon fibers, (ii) conductivenano-sized particles dispersed throughout the matrix resin at theinterlaminar region, and (iii) an uncoated nonwoven carbon veil embeddedin the matrix resin at the interlaminar region, wherein each of theconductive nano-sized particles has at least one dimension smaller thanabout 100 nm, the nonwoven carbon veil is comprised of randomly arrangeduncoated carbon fibers and has an areal weight of about 1 gsm to about10 gsm, and the conductive nano-sized particles and the nonwoven carbonveil are the only conductive components at the interlaminar region. 2.The curable composite material of claim 1, wherein the interlaminarregion further comprises polymeric particles.
 3. The curable compositematerial of claim 2, wherein at least some polymeric particles penetratethrough the nonwoven carbon veil.
 4. The curable composite material ofclaim 2, wherein the polymeric particles is present at a content ofabout 2% to about 20% by weight based on the total weight of the matrixresin in the composite material.
 5. The curable composite material ofclaim 2, wherein the polymeric particles are insoluble thermoplastic orelastomeric particles, and said insoluble particles remain as discreetparticles at the interlaminar region upon curing of the compositematerial.
 6. The curable composite material of claim 5, wherein thepolymeric particles are insoluble thermoplastic particles comprising atleast one thermoplastic polymer selected from the group consisting of:polyimide, polyamideimide, polyamide, polyphthalamide, polyetherketone,polyetheretherketone, polyetherketoneketone, polyaryletherketones,polyphenylenesulfide, liquid crystal polymers, and copolymers thereof.7. The curable composite material of claim 5, wherein the polymericparticles are insoluble elastomeric particles comprising at least onepolymeric material selected from the group consisting of: cross-linkedpolybutadiene, polyacrylic, polyacrylonitrile, and polystyrene.
 8. Thecurable composite material of claim 2, wherein the polymeric particlesare crosslinked particles, each particle comprising one of: (a) acrosslinking network created by crosslinking a cross-linkablethermoplastic polymer having one or more one or more reactive groupswith a cross-linking agent that is chemically reactive to the reactivegroups, and (b) an inter-penetrating polymer network (IPN) comprisingthermoplastic polymer chains intertwined with an independentcrosslinking network, wherein said IPN is created by reacting at leastone compound having one or more reactive groups, a crosslinking agentthat is chemically reactive to the reactive groups, and a thermoplasticpolymer.
 9. The curable composite material of claim 1, wherein theconductive nano-sized particles are carbon-based, nano-sized structuresselected from the group consisting of: carbon nano-tubes (CNTs), carbonnano-fibers, carbon nano-ropes, carbon nano-ribbons, carbonnano-fibrils, carbon nano-needles, carbon nano-sheets, carbon nano-rods,carbon nano-cones, carbon nano-scrolls having scroll-like shapes, carbonnano-ohms, carbon black particles, graphite nano-platelets, graphitenano-dots, graphenes, and combination thereof.
 10. The curable compositematerial of claim 9, wherein the carbon-based, nano-sized structures arecarbon nanotubes (CNTs).
 11. The curable composite material of claim 1,wherein the conductive nano-sized particles are present in an amountwithin the range of about 0.1% to about 10% by weight based on the totalweight of the matrix resin in the composite material.
 12. The curablecomposite material of claim 1, wherein the interlaminar region comprisesa curable matrix resin which is substantially the same as or differentfrom the curable matrix resin impregnating the reinforcement carbonfibers.
 13. The curable composite material of claim 1, wherein thecurable matrix resin impregnating the reinforcing fibers furthercomprises conductive nano-sized particles dispersed throughout.
 14. Thecurable composite material of claim 1, wherein the matrix resinimpregnating the reinforcement fibers comprises one or more thermosetresins.
 15. The curable composite material of claim 14, wherein thethermoset resins are selected from: epoxy resins, imides, vinyl esterresins, cyanate ester resins, phenolic resins, benzoxazines,formaldehyde condensate resins, unsaturated polyesters, and combinationsthereof.
 16. The curable composite material of claim 1, wherein at leastone layer of reinforcement carbon fibers is in the form of continuousunidirectional fibers or a woven fabric.
 17. A curable compositematerial comprising: at least two layers of reinforcement carbon fibersimpregnated with a curable matrix resin; and an interlaminar regionformed between adjacent layers of reinforcement carbon fibers, theinterlaminar region comprising: (i) a curable matrix resin that is thesame as or different from the matrix resin impregnating thereinforcement carbon fibers, (ii) conductive nano-sized particlesdispersed throughout the matrix resin at the interlaminar region, and(iii) an uncoated nonwoven carbon veil embedded in the matrix resin atthe interlaminar region, and (iv) polymeric particles embedded in thematrix resin at the interlaminar region, wherein the conductivenano-sized particles are carbon nanotubes or carbon particles, theconductive nano-sized particles are present in an amount within therange of about 0.1% to about 10% by weight based on the total weight ofthe matrix resin in the composite material, each of the conductivenano-sized particles has dimensions smaller than about 100 nm, thenonwoven carbon veil is comprised of randomly arranged uncoated carbonfibers and has an areal weight of about 1 gsm to about 10 gsm, and theconductive nano-sized particles and the uncoated nonwoven carbon veilare the only conductive components at the interlaminar region.